Q.(a) State and explain Kohlrausch's law of independent migration of ions.
You're viewing a preview — the full solution, concept, methods & PYQ mapping are locked.
Start your 14-day free trial to unlock the full solution →- Kohlrausch's law: limiting molar conductivity is the sum of independent ionic conductivities.
- Molecularity = number of species in an elementary step (theoretical, whole number); order = sum of concentration exponents in the experimental rate law (can be fractional/zero). Bimolecular: 2HI -> H2+I2; trimolecular: 2NO + O2 -> 2NO2.
(a) Kohlrausch's law of independent migration of ions:
Statement: At infinite dilution (when dissociation is complete and interionic effects vanish), each ion migrates independently of the other ions, and the limiting molar conductivity of an electrolyte is the sum of the individual limiting molar conductivities of its constituent cations and anions.
Lambda(0,m) = (nu+) lambda(0,+) + (nu-) lambda(0,-),
where nu+ and nu- are the numbers of cations and anions per formula unit, and lambda(0,+), lambda(0,-) are the limiting molar conductivities of the cation and anion.
Example: Lambda(0) for NaCl = lambda(0, Na+) + lambda(0, Cl-).
Use: it allows calculation of the limiting molar conductivity of weak electrolytes (e.g. acetic acid) which cannot be found by extrapolation.
(b) Molecularity vs order:
Molecularity: It is the number of reacting species (atoms, ions or molecules) that must collide simultaneously in a single elementary step for the reaction to occur. It is always a small whole number (1, 2 or 3), is a theoretical concept, and is defined only for elementary reactions.
Order of reaction: It is the sum of the powers to which the concentration terms are raised in the experimentally determined rate law (rate equation). It is found experimentally, can be zero, fractional or a whole number, and applies to overall (including complex) reactions.
Key differences:
- Molecularity is theoretical (from the mechanism); order is experimental (from the rate law). …
Unlock everything free for 14 days
- Full step-by-step solutions
- Concept-first explanations
- Methods, shortcuts & mistakes
- PYQ mapping + timed mock tests
Full access for 14 days. No credit card required.